EP2214234B1 - Li-ni-based composite oxide particle powder for rechargeable battery with nonaqueous elctrolyte, process for producing the powder, and rechargeable battery with nonaqueous electrolyte - Google Patents

Li-ni-based composite oxide particle powder for rechargeable battery with nonaqueous elctrolyte, process for producing the powder, and rechargeable battery with nonaqueous electrolyte Download PDF

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EP2214234B1
EP2214234B1 EP08849214.5A EP08849214A EP2214234B1 EP 2214234 B1 EP2214234 B1 EP 2214234B1 EP 08849214 A EP08849214 A EP 08849214A EP 2214234 B1 EP2214234 B1 EP 2214234B1
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particles
composite oxide
based composite
oxide particles
hydroxide
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French (fr)
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EP2214234A4 (en
EP2214234A1 (en
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Akihisa Kajiyama
Kazuhiko Kikuya
Teruaki Santoki
Osamu Sasaki
Satoshi Nakamura
Taiki Imahashi
Hideaki Sadamura
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Toda Kogyo Corp
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Toda Kogyo Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to Li-Ni-based composite oxide particles for a non-aqueous electrolyte secondary battery which exhibit a large charge/discharge capacity and are excellent in thermal stability upon charging.
  • LiMn 2 O 4 having a spinel structure
  • LiMnO 2 having a zigzag layer structure
  • LiCoO 2 and LiNiO 2 having a layer rock-salt structure, or the like.
  • LiNiO 2 lithium ion secondary batteries using LiNiO 2 have been noticed because of a large charge/discharge capacity thereof.
  • this material tends to be deteriorated in thermal stability upon charging and charge/discharge cycle durability, and, therefore, it has been required to further improve properties thereof.
  • Ni composite hydroxide particles which are well controlled in properties, crystallinity and contents of impurities, and calcine the particles under the condition which is free from inclusion of Ni 2+ into Li sites thereof.
  • Li-Ni-based composite oxide capable of exhibiting a high packing property, a stable crystal structure and an excellent thermal stability upon charging as a positive electrode active substance for a non-aqueous electrolyte secondary battery.
  • Patent Documents 1 to 5 In order to improve various properties of LiNiO 2 particles such as stabilization of a crystal structure and charge/discharge cycle characteristics, various improving methods have been attempted. For example, it is known that the surface of the respective Li-Ni-based oxide particles is coated with a compound such as lithium manganate (Patent Documents 1 to 5).
  • an Li-Ni-based composite oxide is used as the core material, and an object of the present invention is not to improve the cycle characteristics, but to solve the problems concerning a thermal stability peculiar to the Li-Ni-based composite oxide.
  • Li-Ni-based composite oxide particles As a positive electrode active substance for a non-aqueous electrolyte secondary battery which is improved in thermal stability upon charging.
  • the Li-Ni-based composite oxide capable of fully satisfying the above requirement has not been obtained until now.
  • Patent Document 1 Japanese Patent Application Laid-Open (KOKAI) No. 7-235292
  • the surface of the respective lithium nickelate particles is coated with lithium cobaltate or lithium manganate.
  • the resulting particles tend to fail to exhibit a sufficient thermal stability.
  • Patent Document 2 Japanese Patent Application Laid-Open (KOKAI) No. 9-265985 .
  • LiNiO 2 is used as the core material.
  • the present invention is different from the Patent Document 2 in that different kinds of metal elements are incorporated into the core material of the present invention to form a solid solution therewith for the purpose of enhancing properties of the core material itself.
  • Patent Document 3 Japanese Patent Application Laid-Open (KOKAI) No. 10-236826
  • Patent Document 4 Japanese Patent Application Laid-Open (KOKAI) No. 11-67209
  • the material of the coating layer used in these Patent Documents is constituted of the Li-Co-based composite oxide as a main component and, therefore, different from the material used in the present invention which is constituted of the Li-Ni-based composite oxide as a main component.
  • the Li-Ni-based composite oxide as a core material is coated with a different kind of material.
  • the coating layer has an Li-Mn spinel crystal structure for the purpose of obtaining an active substance having a high output.
  • the coating layer formed therein is different in crystal structure from that of the Patent Document 5, i.e., the coating layer of the present invention is not mainly constituted of the spinel layer.
  • Li-Ni-based composite oxide particles comprising secondary particles of Li-Ni-based oxide particles, Co and/or Al being present therewithin, Li-Mn-based composite oxide being present on a surface of the respective secondary particles, and a concentration of Mn being increased from a center toward a surface of the respective particles, wherein the Li-Mn-based composite oxide has a composition represented by the formula: Li x2 (Mn 1-z2 M2 z2 ) y2 O 2 (where M2 is at least one metal selected from the group consisting of Co, Ni, Al, Fe, Mg, Zr, Ti and B; and x2, y2 and z2 satisfy 1/2 ⁇ x2 ⁇ 4/3, 2/3 ⁇ y2 ⁇ 1 and 0 ⁇ z2 ⁇ 4/5, respectively)
  • the Li-Ni-based composite oxide particles as described above, wherein the secondary particles of the Li-Ni-based oxide particles as core particles have a composition represented by the formula: Li x1 (Ni 1-y1-zl-w1 Co y1 Mn z1 M1 w1 ) O 2 (where x1, y1, z1 and w1 satisfy 0.9 ⁇ x1 ⁇ 1.3, 0.1 ⁇ y1 ⁇ 0.3, 0.0 ⁇ z1 ⁇ 0.3 and 0 ⁇ w1 ⁇ 0.1, respectively; and M1 is at least one metal selected from the group consisting of Al, Fe, Mg, Zr, Ti and B).
  • the Li-Ni-based composite oxide particles as described above, wherein the content of the Li-Mn composite oxide which is coated on the secondary particles of the Li-Ni-based oxide, which form the core particles, is not less than 0.3% by weight to not more than 20% by weight based on the weight of the Li-Ni oxide.
  • the Li-Ni-based composite oxide particles as described above, wherein the average secondary particle diameter of the Li-Ni-based composite oxide particles is 5 to 20 ⁇ m.
  • the Li-Ni-based composite oxide particles as described above, wherein a suspension prepared by suspending the Li-Ni-based composite oxide particles in distilled water has a pH value of not more than 11.5 as measured after allowing the suspension to stand at room temperature.
  • a process for producing the Li-Ni-based composite oxide particles of the invention comprising the steps of allowing an oxide and/or a hydroxide which comprise Mn to mechanically adhere to an Li-Ni-based oxide comprising Co and/or Al; and then heat-treating the obtained material at a temperature of not lower than 400°C and not higher than 1,000°C.
  • a process for producing the Li-Ni-based composite oxide particles of the invention comprising the steps of allowing an oxide and/or a hydroxide which comprise Mn to mechanically adhere to an Ni-based hydroxide comprising Co and/or Al; mixing the obtained material with a lithium compound; and then heat-treating the obtained mixture at a temperature of not lower than 700°C and not higher than 1,000°C in an oxygen-containing atmosphere.
  • a process for producing the Li-Ni-based composite oxide particles of the invention comprising the steps of dropping a manganese-containing solution and an alkali solution to a suspension of Ni-based hydroxide particles comprising Co and/or Al to produce a manganese-containing hydroxide, a manganese-containing oxide hydroxide or a manganese-containing oxide on a surface of a nickel oxide; subjecting the obtained material to washing with water and drying; mixing the dried material with a lithium compound; and then heat-treating the obtained mixture at a temperature of not lower than 700°C and not higher than 1,000°C in an oxygen-containing atmosphere.
  • non-aqueous electrolyte secondary battery comprising the Li-Ni-based composite oxide particles of the invention, as a positive electrode active substance.
  • non-aqueous electrolyte secondary battery wherein when using a negative electrode comprising a material capable of absorbing and desorbing a metallic lithium or a lithium ion, an exothermic peak temperature as measured by differential thermal analysis at a positive electrode under the condition in which the cell is charged to 4.5 V is not lower than 240°C.
  • a positive electrode which comprises Li-Ni-based composite oxide particles of the invention, a conducting agent and a binder.
  • Li-Ni-based composite oxide particles of the invention in a non-aqueous electrolyte secondary battery.
  • Li-Ni-based composite oxide particles when a negative electrode formed from a material capable of absorbing and desorbing a metallic lithium or a lithium ion is used in a cell using the composite oxide particles, an exothermic maximum peak temperature of the cell as measured in the range of 200 to 290°C by differential thermal analysis under the condition that the cell is charged to 4.5 V is shifted to a high-temperature side. As a result, it is possible to enhance a safety of the lithium ion cell.
  • the Li-Ni-based composite oxide particles according to the present invention can exhibit a high discharge capacity at a charge/discharge rate of 0.2 mA/cm 2 irrespective of a high thermal safety thereof.
  • Li-Ni-based composite oxide particles according to the present invention when an Li-Mn-based composite oxide is coated or allowed to be present on or in the vicinity of the surface of respective secondary particles of the Li-Ni-based oxide forming core particles by subjecting these materials to a wet chemical treatment or a dry mechanical treatment, or to further a thermal treatment in addition to the wet or dry treatment, it is possible to produce Li-Ni-based composite particles which can be enhanced in safety upon charging while keeping a high capacity.
  • Li-Ni-based composite oxide particles according to the present invention are suitable as a positive electrode active substance for a non-aqueous electrolyte secondary battery.
  • Li-Ni-based composite oxide particles for a non-aqueous electrolyte secondary battery according to the present invention are described.
  • an Li-Mn-based composite oxide is coated or allowed to be present on or in the vicinity of the surface of respective secondary particles of an Li-Ni-based composite oxide having a specific composition which form core particles.
  • the Li-Ni-based composite oxide particles according to the present invention are intended to involve not only those obtained by coating a whole surface of the secondary particles as the core particles with the Li-Mn-based composite oxide having a specific composition, but also those obtained by allowing the Li-Mn-based composite oxide having a specific composition to be present or adhere in the vicinity of the surface of the secondary particles as the core particles or onto a part of the surface thereof.
  • the Li-Ni-based oxide forming the core particles preferably has a composition represented by the formula: Li x1 (Ni 1-y1-z1-w1 Co y1 Mn z1 M1 w1 ) O 2 (where x1, y1, z1 and w1 satisfy 0.9 ⁇ x1 s 1.3, 0.1 ⁇ y1 s 0.3, 0.0 s z1 ⁇ 0.3 and 0 ⁇ w1 ⁇ 0.1, respectively; and M1 is at least one metal selected from the group consisting of Al, Fe, Mg, Zr, Ti and B).
  • the composition of the Li-Ni-based oxide forming the core particles is out of the above-specified range, it may be difficult to attain a high discharge capacity as a feature of the Li-Ni-based oxide.
  • the particles which are coated or allowed to be present on the core particles have a composition represented by the formula: Li x2 (Mn 1-z2 M2 z2 ) y2 O 2 (where M2 is at least one metal selected from the group consisting of Co, Ni, Al, Fe, Mg, Zr, Ti and B; x2, y2 and z2 satisfy 1/2 ⁇ x2 ⁇ 4/3, 2/3 ⁇ y2 ⁇ 1 and 0 ⁇ z2 ⁇ 4/5, respectively.
  • the thermal stability upon charging may be deteriorated.
  • the concentration of Mn is increased from a center toward the surface of the respective particles.
  • concentration of Mn is uniform over a whole part of the respective secondary particles, it may be difficult to achieve enhancement in a thermal stability thereof while keeping a high cell capacity of the secondary particles as core particles, as aimed by the present invention.
  • concentration of Mn at a central portion of the respective particles is higher than that in a surface portion of the respective secondary particles, it may also be difficult to achieve enhancement in a thermal stability thereof while keeping a high cell capacity of the secondary particles as core particles, as aimed by the present invention.
  • the content of the Li-Mn composite oxide which is coated on the secondary particles of the Li-Ni-based oxide forming the core particles is preferably not less than 0.3% by weight and not more than 20% by weight based on the weight of the Li-Ni oxide.
  • the content of the Li-Mn composite oxide particles which are coated or allowed to be present on the core particles is less than 0.3% by weight, the resulting particles tend to be deteriorated in thermal stability under a charged condition of the cell although they maintain a high discharge capacity.
  • the content of the Li-Mn composite oxide particles which is coated or allowed to be present on the core particles is more than 20% by weight, the resulting particles tend to be deteriorated in discharge capacity although they are improved in thermal stability under a charged condition of the cell.
  • the content of the Li-Mn composite oxide is more preferably 0.4 to 10% by weight and still more preferably 0.5 to 5% by weight.
  • the average secondary particle diameter of the secondary particles forming the core particles is preferably 3 to 20 ⁇ m.
  • the average secondary particle diameter is less than 3 ⁇ m, the resulting particles tend to exhibit a low electrode packing density and a large BET specific surface area, resulting in high reactivity with an electrolyte solution and, therefore, deteriorated thermal stability upon charging.
  • the average secondary particle diameter is more than 20 ⁇ m, the resulting cell tends to suffer from increase in resistance within an electrode owing to increase in thickness of the electrode and, therefore, deterioration in charge/discharge rate characteristics thereof.
  • the average secondary particle diameter of the secondary particles forming the core particles is more preferably 5 to 20 ⁇ m.
  • the average primary particle diameter of the core particles is 0.5 to 1.5 ⁇ m.
  • the core particles necessarily have such an average primary particle diameter at a temperature generally used for calcination of the particles.
  • the average primary particle diameter of the Li-Mn composite oxide which is coated or allowed to be present on the core particles is preferably 0.1 to 3.0 ⁇ m.
  • the particles of the Li-Mn composite oxide necessarily have such an average primary particle diameter at a temperature generally used for calcination of the particles.
  • the average secondary particle diameter of the Li-Ni-based composite oxide particles for a non-aqueous electrolyte secondary battery according to the present invention is preferably 5 to 20 ⁇ m and more preferably 10 to 20 ⁇ m.
  • the average secondary particle diameter of the Li-Ni-based composite oxide particles is less than 5 ⁇ m, the Li-Ni-based composite oxide particles tend to suffer from not only decrease in electrode packing density, but also increase in reactivity with an electrolyte solution owing to increase in BET specific surface area thereof, resulting in deteriorated thermal stability upon charging.
  • the resulting cell tends to suffer from increase in resistance within an electrode owing to increase in thickness of the electrode and, therefore, deterioration in charge/discharge rate characteristics thereof.
  • the Li-Ni-based composite oxide particles according to the present invention preferably have a powder pH value of not more than 11.5.
  • the powder pH value of the Li-Ni-based composite oxide particles is more than 11.5, the resulting particles tends to be deteriorated in thermal stability, or a paint obtained using the particles tends to be undesirably gelled or undergo increase in a viscosity thereof upon forming it into a sheet.
  • the powder pH value of the Li-Ni-based composite oxide particles is determined from a pH value of a suspension as measured by suspending the Li-Ni-based composite oxide particles in distilled water and allowing the resulting suspension to stand at room temperature.
  • an exothermic maximum peak temperature thereof as measured in a differential thermal analysis at a positive electrode under the condition that the cell is charged to 4.5 V is preferably not lower than 240°C.
  • the Li-Ni-based composite oxide particles according to the present invention can be produced by any of (1) a process comprising the steps of allowing an oxide and/or a hydroxide which comprise Mn to mechanically adhere to an Li-Ni-based oxide comprising Co and/or Al; and then heat-treating the obtained material at a temperature of not lower than 400°C and not higher than 1,000°C, (2) a process comprising the steps of allowing an oxide and/or a hydroxide which comprise Mn to mechanically adhere to an Ni-based hydroxide comprising Co and/or Al; mixing the obtained material with a lithium compound; and then heat-treating the obtained mixture at a temperature of not lower than 700°C and not higher than 1,000°C in an oxygen-containing atmosphere, and (3) a process comprising the steps of dropping a manganese-containing solution and an alkali solution to a suspension of Ni-based hydroxide particles comprising Co and/or Al to produce a manganese-containing hydroxide, a manganese-containing oxide hydroxide or
  • the Li-Ni-based oxide particles used as core particles may be produced by any ordinary method such as a solid phase method and a wet synthesis method.
  • the Li-Ni-based oxide particles may also comprise different kinds of metals.
  • the content of Li in the Li-Ni-based oxide particles may be adjusted to be an excessive amount, for example, the content of Li is adjusted to be 0.9 to 1.3 times the amount of the other metals.
  • the content of Li mixed is too small, the resulting particles tend to be deteriorated in capacity.
  • the content of Li mixed is too large, the powder pH value of the resulting Li-Ni-based composite oxide particles tends to be undesirably high.
  • the thus obtained Li-Ni-based oxide particles are adhered with an oxide and/or a hydroxide of a metal element which forms a coating layer thereon.
  • elements other than Mn such as, for example, Al, Fe, Mg, Zr, Ti and B, may be added to the above particles.
  • the adhering method may be conducted by using an apparatus capable of applying a shear force to a powder layer at a high speed.
  • an apparatus capable of applying a shear force to a powder layer at a high speed.
  • examples of such an apparatus include a high-speed shearing mill, a blade-type kneader, a planetary mill, etc.
  • preferred a high-speed shearing mill.
  • Specific examples of the above high-speed shearing mill include "HYBRIDIZER” and "NOBILTA” manufactured by Hosokawa Micron Co., Ltd.
  • the Li-Ni-based oxide particles onto which the oxide and/or hydroxide of the metal element adhere are heat-treated at a temperature of 400 to 1,000°C.
  • the heat-treating temperature is lower than 400°C, the reaction tends to proceed insufficiently, so that the obtained Li-Ni-based composite oxide particles tend to be deteriorated in thermal stability.
  • the heat-treating temperature is higher than 1,000°C, the sintering between the particles tends to occur, and the powder pH value of the obtained Li-Ni-based composite oxide particles tends to become undesirably high.
  • the heat-treating temperature is preferably 500 to 950°C.
  • the above heat treatment may be conducted either in an atmospheric air or in an oxygen gas flow.
  • the Ni-based hydroxide used as core particles may be produced by any ordinary method such as a solid phase method and a wet synthesis method.
  • the Ni-based hydroxide may also comprise different kinds of metals.
  • Ni-based hydroxide particles are adhered with an oxide and/or a hydroxide of a metal element which forms a coating layer thereon.
  • the adhering method may be conducted in the same manner as used in the above production process (1).
  • elements other than Mn such as, for example, Al, Fe, Mg, Zr, Ti and B may be added to the above particles.
  • the mixing ratio of the Li compound to the Ni-based hydroxide particles onto which the oxide and/or hydroxide of the metal element adhere is preferably 0.9 to 1.3.
  • the amount of Li mixed is too small, the resulting particles tend to be deteriorated in capacity.
  • the amount of Li mixed is too large, the powder pH value of the resulting Li-Ni-based composite oxide particles tends to become undesirably high.
  • the resulting mixture is then heat-treated at a temperature of 700 to 1,000°C.
  • the heat-treating temperature is lower than 700°C, the reaction tends to proceed insufficiently, so that the obtained Li-Ni-based composite oxide particles tend to be deteriorated in thermal stability.
  • the heat-treating temperature is higher than 1,000°C, the sintering between the particles tends to occur, and the powder pH value of the obtained Li-Ni-based composite oxide particles tends to become undesirably high.
  • the heat-treating temperature is preferably 750 to 950°C.
  • the above heat treatment is preferably conducted in an oxygen-containing gas atmosphere.
  • the Ni-based hydroxide used as core particles may be produced by any ordinary method such as a solid phase method and a wet synthesis method.
  • the Ni-based hydroxide may also comprise different kinds of metals.
  • Ni-based hydroxide particles are suspended in water, and a solution comprising a metal salt forming a coating layer is added to the resulting suspension. Then, the pH value of the suspension is adjusted to form any of a hydroxide, an oxide hydroxide or an oxide of the metal on the surface of the respective Ni-based hydroxide particles. If required, elements other than Mn such as, for example, Al, Fe, Mg, Zr, Ti and B may be added to the above particles.
  • the mixing ratio of the Li compound to the thus coated Ni-based hydroxide particles is preferably 1.00 to 1.08.
  • the amount of Li mixed is too small, the resulting particles tend to be deteriorated in capacity.
  • the amount of Li mixed is too large, the powder pH value of the resulting Li-Ni-based composite oxide particles tends to become undesirably high.
  • the resulting mixture is then heat-treated at a temperature of 700 to 1,000°C.
  • the heat-treating temperature is lower than 700°C, the reaction tends to proceed insufficiently, so that the obtained Li-Ni-based composite oxide particles tend to be deteriorated in thermal stability.
  • the heat-treating temperature is higher than 1,000°C, the sintering between the particles tends to occur, and the powder pH value of the obtained Li-Ni-based composite oxide particles tends to become undesirably high.
  • the heat-treating temperature is preferably 750 to 950°C.
  • the above heat treatment is preferably conducted in an oxygen-containing gas atmosphere.
  • a conducting agent and a binder are added to the Li-Ni-based composite oxide particles by an ordinary method.
  • the preferred conducting agent include acetylene black, carbon black and graphite.
  • the preferred binder include polytetrafluoroethylene and polyvinylidene fluoride.
  • the secondary battery produced by using the Li-Ni-based composite oxide particles according to the present invention comprises the above positive electrode, a negative electrode and an electrolyte.
  • Examples of a negative electrode active substance which may be used for production of the negative electrode include metallic lithium, lithium/aluminum alloys, lithium/tin alloys, graphite and black lead.
  • a solvent for the electrolyte solution there may be used combination of ethylene carbonate and diethyl carbonate, as well as an organic solvent comprising at least one compound selected from the group consisting of carbonates such as propylene carbonate and dimethyl carbonate, and ethers such as dimethoxyethane.
  • the electrolyte there may be used a solution prepared by dissolving lithium phosphate hexafluoride as well as at least one lithium salt selected from the group consisting of lithium perchlorate and lithium borate tetrafluoride in the above solvent.
  • the secondary battery produced by using the positive electrode active substance comprising the Li-Ni-based composite oxide particles according to the present invention has an initial discharge capacity of not less than 180 mAh/g. Further, the secondary battery exhibits such an excellent thermal stability that an exothermic maximum peak temperature thereof as measured by the below-mentioned method, i.e., as measured in a temperature range of 200 to 290°C by a differential thermal analysis at a positive electrode under the condition that the cell is charged to 4.5 V when using metallic lithium as a negative electrode, is shifted by 15°C or higher towards a high-temperature side.
  • the temperature by which the exothermic maximum peak is shifted towards a high-temperature side is preferably 30°C or higher and more preferably as high as possible.
  • the cell has a low oxygen desorption temperature.
  • the desorption of oxygen in the cell tends to be caused due to desorption of oxygen from the surface of the electrode owing to unstable structure of the cell under a charged condition.
  • an Li-Mn-based composite oxide having a specific composition is allowed to be present on or in the vicinity of the surface of an Li-Ni-based oxide whose secondary particles form core particles and have a specific composition, so that the concentration of Mn in the resulting Li-Ni-based composite oxide particles is increased from a center toward the surface of the respective particles.
  • the resulting composite particles can be enhanced in thermal stability while keeping a high discharge capacity.
  • the Li-Ni-based composite oxide particles according to the present invention when the Li-Mn-based oxide is coated or allowed to be present on or in the vicinity of the surface of the respective secondary particles of the Li-Ni-based oxide forming the core particles by various methods, an exothermic maximum peak thereof as measured in a temperature range of 200 to 290°C by a differential thermal analysis at a positive electrode under the condition that the cell is charged to 4.5 V, is shifted towards a higher-temperature side as compared to the case where the Li-Ni-based oxide forming the core particles was used solely, so that the resulting cell can be improved in safety upon charging.
  • the average particle diameter of the particles is a volume-based average particle diameter as measured by a wet laser method using a laser type particle size distribution measuring apparatus "LMS-30" manufactured by Seishin Kigyo Co., Ltd.
  • the average primary particle diameter of the particles which are coated or present on the core particles was observed and determined using a scanning electron microscope "SEM-EDX” equipped with an energy disperse type X-ray analyzer (manufactured by Hitachi High-Technologies Corp.).
  • the powder pH value of the particles was determined from a pH value of a suspension thereof which was measured by suspending a predetermined amount of the particles in distilled water and then allowing the resulting suspension to stand at room temperature.
  • the coin cell (battery) produced by using the Li-Ni-based composite oxide particles was evaluated for initial charge/discharge characteristics and storage characteristics under a high temperature condition.
  • a metallic lithium blanked into 16 mm ⁇ was used as a negative electrode, and a solution prepared by mixing EC and DMC with each other at a volume ratio of 1:2 in which 1 mol/L of LiPF 6 was dissolved, was used as an electrolyte solution, thereby producing a coin cell of a CR2032 type.
  • the initial charge/discharge characteristics of the cell were determined as follows. That is, under a room temperature condition, the cell was charged at rate of 0.2 mA/cm 2 until reaching 4.25 V and then discharged at a rate of 0.2 mA/cm 2 until reaching 3.0 V to measure an initial charge capacity, an initial discharge capacity and an initial efficiency of the cell.
  • the evaluation for safety of the Li-Ni-based composite oxide particles was carried out as follows. That is, the coin cell of a CR2032 type was produced in the same manner as defined in the above evaluation for initial charge/discharge characteristics, and subjected to initial charge/discharge cycle. Then, the cell was subjected to the second charging at such a current as to complete charging of the cell up to 4.5 V for 10 hr. The coin cell was disassembled while being kept under the above charged condition to dismount the positive electrode therefrom.
  • the positive electrode thus dismounted was received in a sealed state in an SUS pressure cell under the co-existence of the electrolyte solution, and then subjected to differential thermal analysis over the range of from room temperature to 400°C at a scanning speed of 5°C/min.
  • An aqueous solution prepared by mixing 2 mol/L of nickel sulfate with cobalt sulfate at a mixing molar ratio of Ni:Co of 84:16, and a 5.0 mol/L ammonia aqueous solution were simultaneously fed to a reaction vessel.
  • the contents of the reaction vessel were always kept stirred by a blade-type stirrer and, at the same time, the reaction vessel was automatically supplied with a 2 mol/L sodium hydroxide aqueous solution so as to control the pH of the reaction mixture in the reaction vessel to 11.5 ⁇ 0.5.
  • the Ni-Co hydroxide thus produced in the reaction vessel was overflowed therefrom through an overflow pipe, and collected in a concentration vessel connected to the overflow pipe to concentrate the Ni-Co hydroxide.
  • the concentrated Ni-Co hydroxide was circulated to the reaction vessel, and the reaction was continuously carried out for 40 hr until the concentration of the Ni-Co hydroxide in the reaction vessel and a precipitation vessel reached 4 mol/L.
  • the resulting suspension was withdrawn from the reaction vessel, and washed with water in an amount of 5 times the amount of the suspension using a filter press, and further subjected to deaggregation to adjust a concentration of the Ni-Co hydroxide in the suspension to 0.2 mol/L.
  • a 0.2 mol/L sodium aluminate aqueous solution was continuously fed to the suspension in the reaction vessel such that a molar ratio of (Ni+Co):Al in the resulting mixture was 95:5.
  • the contents of the reaction vessel were always kept stirred by the stirrer and, at the same time, a 0.2 mol/L sulfuric acid aqueous solution was automatically supplied thereto so as to control the pH of the reaction mixture of the reaction vessel to 10.5 ⁇ 0.5, thereby obtaining a suspension comprising the Ni-Co hydroxide coated with aluminum hydroxide.
  • the resulting Al-coated Ni-Co hydroxide particles were mixed with lithium hydroxide monohydrate whose particle size was previously controlled by a crusher, such that a molar ratio of Li/(Ni+Co+Al) in the resulting mixture was 1.02.
  • the resulting mixture was calcined in an oxygen atmosphere at 750°C for 10 hr, and then deaggregated and pulverized.
  • the obtained calcined product had a chemical composition of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 and an average particle diameter of 16 ⁇ m.
  • the thus obtained Li-Ni-based oxide was used as secondary particles forming core particles.
  • the thus obtained Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 forming the core particles was mixed with Mn 3 O 4 such that the amount of Mn 3 O 4 mixed was 2% by weight based on the weight of the core particles, and the resulting mixture was subjected to mechanical treatment using a mechanical crusher for 30 min, and then calcined again in an oxygen atmosphere at 800°C for 5 hr, thereby obtaining Li-Ni-based composite oxide particles comprising secondary particles of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 forming the core particles whose surface was coated with 2% by weight of Li 2 MnO 3 . At this time, it was confirmed that the average particle diameter (D 50 ) of the resulting composite oxide particles was 16 ⁇ m. As a result of subjecting the thus obtained Li-Ni-based composite oxide particles to X-ray diffraction analysis, it was confirmed that the Li-Ni-based oxide and Li 2 MnO 3 were present therein, but no other different phases were observed.
  • the Li-Ni-based composite oxide particles were suspended in distilled water to prepare a 2 wt% suspension thereof, and the pH value of the resulting suspension was measured at room temperature. As a result, it was confirmed that the pH value of the suspension was 11.3. Further, as a result of subjecting a secondary battery produced using the Li-Ni-based composite oxide particles to differential thermal analysis at a positive electrode thereof under the condition that the cell was charged to 4.5 V, it was confirmed that an exothermic maximum peak temperature thereof (DSC) was 248°C. In addition, it was also confirmed that the discharge capacity (1-DCH) of the secondary battery using the Li-Ni-based composite oxide particles as a positive electrode active substance was 175 mAh/g.
  • Ni-Co hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained hydroxide particles were mixed with Mn 3 O 4 particles such that the amount of Mn 3 O 4 mixed was 0.5% by weight based on the weight of the hydroxide particles, and the resulting mixture was subjected to mechanical treatment using a mechanical crusher for 30 min, thereby obtaining a composite material.
  • the thus obtained composite material was mixed with lithium hydroxide monohydrate such that the molar ratio of Li/(Ni + Co + Al) was 1.02.
  • Li-Ni-based composite oxide particles comprising secondary particles of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 whose surface was coated with 0.5% by weight of Li 2 MnO 3 .
  • the pH value of the thus obtained Li-Ni-based composite oxide particles as measured by the same method as defined in Example 1 was 11.4.
  • an exothermic maximum peak temperature thereof was 250°C, and the discharge capacity of the Li-Ni-based composite oxide particles was 175 mAh/g.
  • Ni-Co hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained hydroxide particles were suspended in pure water, and then manganese sulfate was dissolved in the resulting suspension such that the amount of manganese sulfate dissolved corresponded to 0.5% by weight in terms of Mn 3 O 4 particles based on the weight of the hydroxide particles.
  • the thus obtained suspension was titrated with 0.1N NaOH to precipitate a hydroxide of Mn on the surface of the Ni-Co-Al hydroxide.
  • the obtained suspension was washed with water in an amount of 10 times the weight of the Ni-Co hydroxide using a filter press, and then dried, thereby obtaining an Ni-Co-Al-Mn composite material.
  • the thus obtained composite material was mixed with lithium hydroxide monohydrate such that the molar ratio of Li/(Ni + Co + Al) was 1.02.
  • Li-Ni-based composite oxide particles comprising secondary particles of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 whose surface was coated with 0.5% by weight of Li 2 MnO 3 .
  • Ni-Co hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained Al-coated Ni-Co hydroxide particles were mixed with lithium hydroxide monohydrate whose particle size was previously adjusted by a crusher such that the molar ratio of Li/(Ni + Co + Al) was 1.08.
  • the resulting mixture was then calcined in an oxygen atmosphere at 750°C for 10 hr, and then deaggregated and pulverized.
  • the obtained calcined product had a chemical composition of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 and an average particle diameter of 20 ⁇ m.
  • the thus obtained Li-Ni-based oxide was used as secondary particles forming core particles.
  • the Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 forming the core particles was mixed with Mn 3 O 4 such that the amount of Mn 3 O 4 mixed was 5% by weight based on the weight of the core particles.
  • the resulting mixture was subjected to mechanical treatment using a mechanical crusher for 30 min, and then calcined again in an oxygen atmosphere at 800°C for 5 hr, thereby obtaining Li-Ni-based composite oxide particles comprising secondary particles of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 forming the core particles whose surface was coated with Li 2 MnO 3 .
  • Ni-Co hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained hydroxide particles were mixed with Mn 3 O 4 particles such that the amount of Mn 3 O 4 mixed was 5% by weight based on the weight of the hydroxide particles, and the resulting mixture was subjected to mechanical treatment using a mechanical crusher for 30 min, thereby obtaining a composite material.
  • the thus obtained composite material was mixed with lithium hydroxide monohydrate such that the molar ratio of Li/(Ni + Co + Al) was 1.08.
  • Li-Ni-based composite oxide particles comprising secondary particles of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 whose surface was coated with 5% by weight of Li 2 MnO 3 .
  • Ni-Co hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained hydroxide particles were suspended in pure water, and then manganese sulfate was dissolved in the resulting suspension such that the amount of manganese sulfate dissolved corresponded to 5% by weight in terms of Mn 3 O 4 particles based on the weight of the hydroxide particles.
  • the thus obtained suspension was titrated with 0.1N NaOH to precipitate a hydroxide of Mn on the surface of the respective Ni-Co-Al hydroxide particles.
  • the obtained suspension was washed with water in an amount of 10 times the weight of the Ni-Co hydroxide using a filter press, and then dried, thereby obtaining an Ni-Co-Al-Mn composite material.
  • the thus obtained composite material was mixed with lithium hydroxide monohydrate such that the molar ratio of Li/(Ni + Co + Al) was 1.08.
  • Li-Ni-based composite oxide particles comprising secondary particles of Li 1.08 Ni 0.8 Co 0.15 Al 0.05 O 2 whose surface was coated with 5% by weight of Li 2 MnO 3 .
  • Ni-Co-Mn hydroxide particles having a compositional ratio of Ni:Co:Mn of 50:20:30 and an average secondary particle diameter of 14.5 ⁇ m were mixed with lithium hydroxide monohydrate such that the molar ratio of Li/(Ni + Co + Mn) was 1.02.
  • the resulting mixture was calcined in an oxygen atmosphere at 950°C for 15 hr, thereby obtaining a composite oxide having a chemical composition of Li 1.02 Ni 0.5 Co 0.2 Mn 0.3 O 2 .
  • the thus obtained composite oxide was mixed with a composite hydroxide having a molar ratio of Co/Mn of 9/1 such that the amount of the hydroxide mixed was 3% by weight based on the weight of the composite oxide.
  • the resulting mixture was subjected to mechanical treatment using a mechanical crusher for 30 min, and then calcined again in an oxygen atmosphere at 850°C for 5 hr, thereby obtaining Li-Ni-based composite oxide particles comprising secondary particles of Li 1.02 Ni 0.5 Co 0.2 Mn 0.3 O 2 forming the core particles whose surface was coated with 3% by weight of LiMn 0.1 Co 0.9 O 2 .
  • the thus obtained Li-Ni-based composite oxide particles were suspended in distilled water to prepare a 2 wt% suspension thereof, and the pH value of the resulting suspension was measured at room temperature. As a result, it was confirmed that the pH value of the suspension was 11.2. Further, as a result of subjecting the Li-Ni-based composite oxide particles to differential thermal analysis under the condition that the cell using the composite oxide particles was charged to 4.5 V, it was confirmed that an exothermic maximum peak temperature thereof was 232°C. In addition, it was also confirmed that the discharge capacity of the Li-Ni-based composite oxide particles was 175 mAh/g.
  • Ni-Co-Al composite hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained composite hydroxide particles were mixed with lithium hydroxide monohydrate whose particle size was previously adjusted by a crusher such that the molar ratio of Li/(Ni + Co + Al) was 1.02.
  • the resulting mixture was calcined in an oxygen atmosphere at 750°C for 10 hr, and then deaggregated and pulverized.
  • the obtained calcined product had a chemical composition of Li 1.02 Ni 0.8 Co 0.15 Al 0.05 O 2 and an average particle diameter of 16 ⁇ m.
  • the thus obtained Li-Ni-based composite oxide particles were suspended in distilled water to prepare a 2 wt% suspension thereof, and the pH value of the resulting suspension was measured at room temperature. As a result, it was confirmed that the pH value of the suspension was 11.5. Further, as a result of subjecting the Li-Ni-based composite oxide particles to differential thermal analysis under the condition that the cell using the composite oxide particles was charged to 4.5 V, it was confirmed that an exothermic maximum peak temperature thereof was 236°C. In addition, it was also confirmed that the discharge capacity of the Li-Ni-based composite oxide particles was 175 mAh/g.
  • Ni-Co-Al composite hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained composite hydroxide particles were mixed with lithium hydroxide monohydrate whose particle size was previously adjusted by a crusher such that the molar ratio of Li/(Ni + Co + Al) was 1.02.
  • the resulting mixture was calcined in an oxygen atmosphere at 750°C for 10 hr, and then deaggregated and pulverized.
  • the obtained calcined product had a chemical composition of Li 1.02 Ni 0.80 Co 0.15 Al 0.05 O 2 and an average particle diameter of 16 ⁇ m.
  • the thus obtained calcined product was mixed with Li 2 MnO 3 particles such that the amount of the Li 3 MnO 3 particles mixed was 0.5% by weight based on the weight of the calcined product.
  • the resulting mixed particles were suspended in distilled water to prepare a 2 wt% suspension thereof, and the pH value of the resulting suspension was measured at room temperature. As a result, it was confirmed that the pH value of the suspension was 11.5. Further, as a result of subjecting the Li-Ni-based composite oxide particles to differential thermal analysis under the condition that the cell using the composite oxide particles was charged to 4.5 V, it was confirmed that an exothermic maximum peak temperature thereof was 236°C. In addition, it was also confirmed that the discharge capacity of the Li-Ni-based composite oxide particles was 173 mAh/g.
  • Ni-Co-Al composite hydroxide particles coated with aluminum hydroxide which had a compositional ratio of Ni:Co:Al of 80:15:5 and an average secondary particle diameter of 14.5 ⁇ m were produced in the same manner as defined in Example 1.
  • the thus obtained composite hydroxide particles were mixed with lithium hydroxide monohydrate whose particle size was previously adjusted by a crusher such that the molar ratio of Li/(Ni + Co + Al) was 1.02.
  • the resulting mixture was calcined in an oxygen atmosphere at 750°C for 10 hr, and then deaggregated and pulverized.
  • the obtained calcined product had a chemical composition of Li 1.02 Ni 0.80 Co 0.15 Al 0.05 O 2 and an average particle diameter of 16 ⁇ m.
  • the calcined product was mixed with a composite hydroxide having a molar ratio of Ni/Mn of 9/1 such that the amount of the composite hydroxide mixed was 3% by weight based on the weight of the calcined product.
  • the resulting mixture was subjected to mechanical treatment using a mechanical crusher for 30 min, and then calcined again in an oxygen atmosphere at 850°C for 5 hr, thereby obtaining Li-Ni-based composite oxide particles comprising secondary particles of Li 1.02 Ni 0.5 Co 0.2 Al 0.3 O 2 forming the core particles whose surface was coated with 3% by weight of LiMn 0.1 Co 0.9 O 2 .
  • the resulting mixed particles were suspended in distilled water to prepare a 2 wt% suspension thereof, and the pH value of the resulting suspension was measured at room temperature. As a result, it was confirmed that the pH value of the suspension was 11.2. Further, as a result of subjecting the Li-Ni-based composite oxide particles to differential thermal analysis under the condition that the cell using the composite oxide particles was charged to 4.5 V, it was confirmed that an exothermic maximum peak temperature thereof was 230°C. In addition, it was also confirmed that the discharge capacity of the Li-Ni-based composite oxide particles was 175 mAh/g.
  • the Li-Ni-based composite oxide particles were produced by variously changing the composition of the core particles for the Li-Ni-based composite oxide particles, the composition and weight percentage of the particles which were coated or allowed to be present on or in the vicinity of the surface of the respective core particles, and the calcination temperature.
  • Table 1 Various properties of the thus obtained Li-Ni-based composite oxide particles are shown in Table 1.
  • the Li-Ni-based composite oxide particles obtained in Examples 1 to 6 all exhibited an exothermic maximum peak higher than that of the core particles (i.e., shifted to a higher-temperature side).
  • the Li-Ni-based composite oxide particles according to the present invention are inhibited from undergoing the reaction with an electrolyte solution upon charging, and, therefore, can provide a positive electrode material having an excellent thermal stability.
  • Li-Ni-based composite oxide particles obtained in Examples 1 to 6 all exhibited an initial discharge capacity of not less than 170 mAh/g, and, therefore, can provide a positive electrode material having a high discharge capacity.
  • the Li-Ni-based composite oxide particles according to the present invention exhibit a large charge/discharge capacity and are, therefore, effective as an active substance for a non-aqueous electrolyte cell which has an excellent thermal stability upon charging.
EP08849214.5A 2007-11-12 2008-11-11 Li-ni-based composite oxide particle powder for rechargeable battery with nonaqueous elctrolyte, process for producing the powder, and rechargeable battery with nonaqueous electrolyte Active EP2214234B1 (en)

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